Efficient Imine Formation by Oxidative Coupling at Low Temperature Catalyzed by High-Surface-Area Mesoporous CeO2 with Exceptional Redox Property

High-surface-area mesoporous CeO₂ (hsmCeO₂) was prepared by a facile organic-template-induced homogeneous precipitation process and showed excellent catalytic activity in imine synthesis in the absence of base from primary alcohols and amines in air atmosphere at low temperature. For comparison, ordinary CeO₂ and hsmCeO₂ after different thermal treatments were also investigated. XRD, N₂ physisorption, UV-Raman, H₂ temperature-programmed reduction, O₂ temperature-programmed desorption, EPR spectroscopy, and X-ray photoelectron spectroscopy were used to unravel the structural and redox properties. The hsmCeO₂ calcined at 400 °C shows the highest specific surface area (158 m² g⁻¹), the highest fraction of surface coordinatively unsaturated Ce³⁺ ions (18.2 %), and the highest concentration of reactive oxygen vacancies (2.4×10¹⁵ spins g⁻¹). In the model reaction of oxidative coupling of benzyl alcohol and aniline, such an exceptional redox property of the hsmCeO₂ catalyst can boost benzylideneaniline formation (2.75 and 5.55 mmol h⁻¹ based on >99 % yield at 60 and 80 °C, respectively) in air with no base additives. It can also work effectively at a temperature of 30 °C and in gram-scale synthesis. These are among the best results for all benchmark ceria catalysts in the literature. Moreover, the hsmCeO₂ catalyst shows a wide scope towards primary alcohols and amines with good to excellent yield of imines. The influence of reaction parameters, the reusability of the catalyst, and the reaction mechanism were investigated.     

Artificial Genetic Sets Composed of Size‐Expanded Base Pairs

We describe in this Minireview the synthesis, properties, and applications of artificial genetic sets built from base pairs that are larger than the natural Watson–Crick architecture. Such designed systems are being explored by several research groups to investigate basic chemical questions regarding the functions of the genetic information storage systems and thus of the origin and evolution of life. For example, is the terrestrial DNA structure the only viable one, or can other architectures function as well? Working outside the constraints of purine–pyrimidine geometry provides more chemical flexibility in design, and the added size confers useful properties such as high binding affinity and helix stability as well as fluorescence. These features are useful for the investigation of fundamental biochemical questions as well as in the development of new biotechnological, biomedical, and nanostructural tools and methods.